Treatment of cellulosic fibers with certain chloroamines and chloroquaternaries



United States Patent 3,510,248 TREATMENT OF CELLULOSIC FIBERS WITHCERTAIN CHLOROAMINES AND CHLOROQUATERNARIES Jean B. Thielen and James L.Keen, New Brighton, and Lyle F. Elmquist, North St. Paul, Minn.,assignors to General Mills, Inc., a corporation of Delaware No Drawing.Filed Feb. 8, 1967, Ser. No. 614,554 Int. Cl. D06m 13/34 US. Cl.8--116.2 12 Claims ABSTRACT OF THE DISCLOSURE Cellulosic fibers aretreated with chloroamines and chloroquaternaries to improve the softnessand/or water repellency thereof, said chloramines and chloroquaternarieshaving the general formulae The present invention relates to the processof treating cellulosic fibers with certain chloroamines andchloroquaternaries and to the resulting treated fibers. Moreparticularly, it relates to the method of improving the softness and/ orwater repellency of cellulosic fibers by treating same with certainchloroamines and chloroquaternaries.

A number of fatty compounds have been used in the past for textilesoftening purposes. One such compound in use at the present time isdimethyl difatty quaternary ammonium chloride, in which the fatty groupis predominantly a C saturated groupi.e. stearyl. While these compoundsdo soften textiles, particularly those derived from cellulosic fibers,such softening is far from permanent and thus the said quaternaries areordinarily added to the textiles at each washing. It would be highlydesirable to eliminate the need to add softening agents each and everytime the fabric is washed.

It is, therefore, an object of our invention to provide a process oftreating cellulosic fibers to improve the softness and/or Waterrepellency thereof. It is a further object of the invention to provide amethod of treating cellulosic fibers with certain chloramines andchloroquaternaries. Another object of the invention is to providecellulosic fibers of improved softness and/ or water repellency. Theseand other objects will become apparent from the following detaileddescription.

We have now discovered that cellulosic fibers can be treated withcertain chloroamines or chloroquaternaries to yield treated fibers withimproved and relatively permanent softness and/ or water repellency.While We do not wish to be bound by the following theory, it is believedthat the fatty groups of the chloroamines and chloroquaternariesemployed provide the softening and water repellency and that suchdesirable improvements are made relatively permanent by the reaction ofthe hydroxy groups of the fibers and the chlorine groups of thechloroamines and chloroquaternaries. Thus the fatty amine moiety and thefatty quaternary moiety are attached to the fibers through etherlinkages.

The chloroamines and chloroquaternaries useful in the practice of thepresent invention have the following idealized, general formulae:

where R is a saturated or mono or polyolefinically unsaturated aliphatichydrocarbon group of from 8 to 24 carbon atoms, R is an alkyl group of 1to 4 carbon atoms or a saturated or mono or polyolefinically unsaturatedaliphatic hydrocarbon group of from 8 to 24 carbon atoms, R is an alkylgroup of 1 to 4 carbon atoms and R, is a divalent alkylene or alkyleneether group containing from 2 to about 12 carbon atoms. Representativealiphatic hydrocarbon group (R R are octyl, octenyl, nonyl, decyl,decenyl, dodecyl, dodecenyl, ethyldodecyl, tridecyl, hexadecyl,octadecyl, methyloctadecyl, octadecenyl and the like. Representativealkyl groups (R R are methyl, ethyl, propyl, butyl, isobutyl and thelike. Representative alkylene or alkylene ether groups (R are --CH -CHCH CH CH OCH CH butylene, isobutylene, pentylene, heptylene, octylene,decylene, and the like.

It is preferred that the aliphatic hydrocarbon group (R is a saturated,straight chained group of 12 to 24 carbon atoms, that the alkyl group (RR is methyl and that R; is an alkylene ether group-especially It is alsopreferred that R is a saturated, straight chained group of 12 to 24carbon atoms. As the chain length of R or R and R is reduced to below 12carbon atoms, the ability of the chloroamines and chloroquaternaries toprovide softness and/or water repellency is also reduced somewhat. Thuscompounds Where R or R and R are aliphatic hydrocarbon groups of 8 to 11carbon atoms are less preferred treating agents. However, when fiberstreated with such shorter chain length compounds are washed in asolution of an anionic detergent, the softness and/or water repellencyis generally increased as is also the case with the longer chain lengthchloroamines and chloroquaternaries. Apparently, the anionic detergentcomplexes with the amine or quaternary moieties attached to the fibersand the resulting complex containing fibers have generally furtherimproved softness and/or water repellency.

The chloroamines are prepared by reacting a secondary amine with analkylene dichloride or an alkylene ether dichloride. Thechloroquaternaries are prepared by reacting a tertiary amine with thealkylene dichloride or alkylene ether dichloride. Secondary and tertiaryamines having the groups R R and R defined above may be employed. Thealkylene dichloride or alkylene ether dichloride employed is oneproviding the group R defined above.

Representative secondary amines are methylstearyl, methyldecyl,methyloctyl, methyldodecyl, ethylstearyl, ethyldecyl, ethyldodecyl,methyllauryl, methylmyristyl, methylpalmityl, methyloleyl,methyllinoleyl, methyltallow, methyl(hydrogenated tallow), dioctyl,dioctenyl, didodecyl, didecyl, dihexadecyl, dilauryl, .dimyristyl,dipalmityl, dioleyl, dilinoleyl, di(hydrogenated tallow) and the like.

Representative tertiary amines are dimethylstearyl, dimethyldecyl,dimethyldodecyl, diethylstearyl, diethyldecyl, diethyldodecyl,dimethyloctyl, dimethyllauryl, dimethylmyristyl, dimethylpalmityl,dimethyloleyl, dimethyllinoleyl, dimethyltallow, dimethyl(hydrogenatedtallow),

and

3 methyldioctyl, methyldioctenyl, ethyldioctyl, methyldidecyl,methyldidodecyl, ethyldidodecyl, methyldihexadecyl, methyldilauryl,methyldimyristyl, methyldipalmityl, methyldioleyl, methyldilinoleyl,methyldi(hydrogenated tallow) and the like. the term tallow whereverused refers to the mixture of hydrocarbon radicals derived from themixture of fatty acids obtained from tallow. The term hydrogenatedtallow refers to such mixtures of radicals which are essentiallysaturated and consist mainly of the stearyl and palmityl radicals.

Representative alkylene dichlorides and alkyllene ether dichlorides aretrimethylene dichloride, tetramethylenc dichloride, 2,2'-dichlorodiethylether, dichloroisopropyl ether, decamethylene dichloride and the like.

The described chloroamines and chloroquaternaries are prepared by slowlycontacting the secondary or tertiary amine with an excess of thedichloride compounds. This reaction is preferably carried out attemperatures of about 100 C. to 150 C. After completion of the reactionthe excess dichloride which also acts as the reaction solvent is removedsuch as by distillation or the like. The product can then berecrystallized from ethyl acetate if desired. The reactions can beillustrated as follows using 2,2'-dichlorodiethyl ether andmethyldodecyl amine and dimethyldodecyl amine:

The preparation of the chloroamines and chloroquaternaries useful in thepresent invention is further illustrated by the following examples:

EXAMPLE A Two hundred eighty six grams (2 moles) of dichloroethyl etherand 16.8 g. (0.2 moles) NaHCO were added to a reaction flask fitted witha stirrer and heated to 110 C. One hundred five grams (0.2 mole)di(hydrogenated tallow) methyl amine were then slowly added withstirring over a one half hour period. Heating and stirring was continuedfor about six hours during which time the highest temperature reachedwas 130 C. Excess dichloroethyl ether was removed and the product wasrecrystallized from ethyl acetate. There was obtained 94.3 g. of a solidwhite product which consisted essentially of the chloroquaternary havingthe formula:

CH [R1N CHzCH2OCH2CH2Cl :]o1

where R and R are hydrogenated tallow.

EXAMPLE B Example A is essentially repeated using methyl (hydrogenatedtallow) amine. There is obtained the corresponding chloroaminecontaining the group.

The chloroamines and chloroquaternaries are useful in treatingcellulosic fibers or articles prepared from such fibers alone or incombination with noncellulosic fibers such as nylon, polyester fibersand the like. The invention is particularly applicable to the treatmentof woven cellulosic textile materials. However, fibrous sheets, pads,

films and the like, laid down from cellulose fibers can be treated eventhough in a nonwoven form.

The cellulosic fibers can be treated with the chloroquaternaries andchloroamines by various methods. A preferred method is to immerse thefibers or articles (i.e. fabrics) derived therefrom in an aqueoussolution or emulsion of the said chloroamines or chloroquaternaries. Thesaturated fibers or articles are then dried and cured at temperatures inthe range of about C. to about 140 C. Curing temperatures of C. to C.are preferred. The reaction between the cellulosic fibers and thechloroamines or chloroquaternaries is catalyzed by sodium hydroxide. Thesodium hydroxide apparently reacts with the cellulosic hydroxyl groupsto yield -ONa groups. The latter groups then apparently react with theCl-R groups to yield OR linkages and NaCl.

The sodium hydroxide can be added to the fiber, the aqueous treatingsolution or after the chloroamine or chloroquaternary has been broughtinto contact with the fiber. One preferred method is to pretreat thefibers with an aqueous solution of NaOH. Another preferred procedure isto add the NaOH to the aqueous solution or emulsion of the chloroamineor chloroquaternary and then immerse the fibers in such compositetreating solution. The NaOH catalyst can be used in widely varyingamounts such as from about 0.01 to 15% by weight and higher based on thedry weight of the cellulosic fibers or articles derived therefrom. Thehigher levels of NaOH are preferably used when the fibers arepretreatedi.e. the NaOH is added to the fibers prior to the addition ofthe chloroamine or chloroquaternary. The use of aqueous solutions oremulsions of the chloroamines or chloroquaternaries is preferred inorder to obtain a fairly even distribution of the said compounds on thefibers or articles. In addition, the water is readily removed by drying,such as during the curing step.

The chloroamines and chloroquaternaries are used in an amount suflicientto improve the softness and/or water repellency of the cellulosicfibers. Preferably, the compounds are used in an amount of about 0.05 to10% by weight based on the dry Weight of the fibers. Amounts of about0.5 to 2.5% by weight are especially preferred. At the higher levels,the fibers have increased softness levels, the fibers have increasedsoftness and a considerable amount of water repellency. At the lowerlevels, the fibers have increased softness and a considerable amount ofwater repellency.

The following specific description further illustrates the presentinvention.

EAMPLE 1 The chloroquaternary of Example A was dissolved in a 1.0% byweight aqueous NaOH solution at a level of 1% by weight. Birdseye cottonswatches (36" by 12") were irnrrnersed in an excess of the treatingsolution with agitation for one minute at room temperature and thenwrung out to a 100% by weight Wet pickup based on the dry weight of thecloth. The swatches were then dried and cured 15 minutes at 100 C.Following this curing step, the swatches were rinsed in water to removeNaOH and again dried. The speciments of cotton thus treated were verysoft and water repellent as compared to an untreated control. Repeatedwashing of such treated swatches using the nonionic detergent All didnot reduce the fine properties of the cloth. When the swatches werestained with bromphenol blue, a blue complex was formed with thequaternary moiety indicating the permanency of the treatment.

EXAMPLE 2 Example 1 was repeated except that no NaOH was included in thetreating solution and the cotton swatches were pretreated with NaOH.Thus the swatches were im mersed in an approximately 15% by weightaqueous NaOH solution for one minute at room temperature followed bywringing out to about 200% wet pickup based on the dry weight of thecloth. The pretreated swatches were then immersed in chloroquaternarysolution, dried and cured as in Example 1. The swatches had essentiallythe same fine properties as those prepared in Example 1. Repeatedwashing of such swatches using All did, however, lower the waterrepellency a small amount.

Softening and/or Water repellency is also obtained by treating thecellulosic fibers as in Examples 1 and 2 with various of the otherdescribed chloroamines and chloroquaternaries such as those compoundsobtained by reacting hexamcthylene dichloride or 2,2'dichloroethyl etherwith methyldodecyl amine, methyl(hydrogenated tallow) amine,methyldidodecyl amine and the like.

While specific examples of the invention have been described, it will beevident that other variations of the invention are possible within thescope of the following claims.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. A process of treating cellulose fibers which comprises contactingsaid fibers with a compound selected from chloroamines andchloroquaternaries in an amount suflicient to improve the softnessand/or water repellency of the fibers and curing the fibers, saidchloroamines and chloroquaternaries having the formulae:

'M Rz-N-Rr-Cl and where R is an aliphatic hydrocarbon group of from 8 to24 carbon atoms, R is an alkyl group of 1 to 4 carbon atoms or analiphatic hydrocarbon group of from 8 to 24 carbon atoms, R is an alkylgroup of 1 to 4 carbon atoms and R is an alkylene or alkylene ethergroup containing from 2 to about 12 carbon atoms.

2. The process of claim 1 wherein the cellulosic fibers are in the formof a woven fabric.

3. The process of claim 1 wherein the cellulosic fibers are contactedwith the compound by immersing the former in an aqueous solution oremulsion of the latter.

4. The process of claim 1 wherein the compound is used in amount ofabout 0.05 to by weight based on the dry weight of the cellulosicfibers.

5. The process of claim 1 wherein the curing of the fiber-compound iscarried out at temperatures of about C. to C.

6. The process of claim 1 wherein R is an aliphatic hydrocarbon group of8 to 24 carbon atoms.

7. The process of claim 1 wherein R and R are aliphatic hydrocarbongroup of 12 to 24 carbon atoms.

8. The process of claim 1 wherein the compound is a chloroquaternary andwherein R and R are saturated, straight chain hydrocarbon groups of 12to 24 carbon atoms, R is methyl and R is 9. The process of claim 7wherein the compound is a chloroamine.

10. The process of claim 1 wherein the cellulosic fibers are in the formof a woven fabric, the contacting is carried out by immersing the fabricin an aqueous solution of the compound, the aqueous solution containsNaOH as a catalyst, the compound is a chloroquaternary, thechloroquaternary is used in an amount of about 0.05 to 10% by weightbased on the dry weight of the fabric, the curing is carried out at atemperature of about 90 C. to 140 C., and R and R are aliphatichydrocarbon groups of 12 to 24 carbon atoms.

11. The process of claim 10 wherein R and R is CH CH -OCH CH 12. Thetreated cellulosic :fibers prepared by the process of claim 1.

References Cited UNITED STATES PATENTS 2,216,958 10/1940 lPannwitz etal. 884 XR 2,370,031 2/ 1945 Graenacher et a1. 8116.2 2,623,041 12/ 1952Grassie 8-l16.2 XR

OTHER REFERENCES H. A. Schuyten, J. David Reid, J. W. Weaver, and JohnG. Frick, Jr.: Imparting Water Repellency to T extiles by ChemicalMethods: A Review of the Literature, Textile Research Journal, vol. 18,1948, pp. 396-397.

GEORGE F. LESM-ES, Primary Examiner J. R. MILLER, Assistant ExaminerU.S. Cl. X.R.

22 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,510,28 Dated May 5, 97

Invencofls) Jean B. Thielen, James L. Keen and Lyle F. Elmquist It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 1, line 4 "chlor'amines should read --chloroamines-- Column 2,line 1 "group" should read "groups"; line 20 insert a comma after lastformula; line 21 "-CH CH CH-O" should read -CH CH CH -O line 21 insert acomma after last formula. Column line 5 like the term should read--like. The term--. Column 4, lines ML and 45 cancel levels, the fibershave increased softness and a considerable amount of" and insert --butgreatly increased--; line 61 "speciments" should read --specimens--.Column 5, line 22 "cellulose" should read --cellulos'1c--. Column 6,line 2 after "compound" insert --c0mb1nation--; line 25 after "R3"insert --is methyl.

mama Am) SEALED B Am and nm mm 2. mm, 38. neafin Offioer Gomtissioner ofPatents

